WO2019171603A1 - Cell, cell stack, redox flow battery, and redox flow battery system - Google Patents
Cell, cell stack, redox flow battery, and redox flow battery system Download PDFInfo
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- WO2019171603A1 WO2019171603A1 PCT/JP2018/009349 JP2018009349W WO2019171603A1 WO 2019171603 A1 WO2019171603 A1 WO 2019171603A1 JP 2018009349 W JP2018009349 W JP 2018009349W WO 2019171603 A1 WO2019171603 A1 WO 2019171603A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
- H01M8/04604—Power, energy, capacity or load
- H01M8/04619—Power, energy, capacity or load of fuel cell stacks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04664—Failure or abnormal function
- H01M8/04686—Failure or abnormal function of auxiliary devices, e.g. batteries, capacitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
- H01M8/04753—Pressure; Flow of fuel cell reactants
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a cell, a cell stack, a redox flow battery, and a redox flow battery system.
- Patent Documents 1 and 2 include a cell that performs charging / discharging with an electric power system, a tank that stores an electrolytic solution supplied to the cell, a circulation pump that circulates the electrolytic solution between the cell and the tank, A redox flow battery system including an AC / DC converter (power converter) arranged between a cell and a power system is disclosed.
- AC / DC converter power converter
- the cell of the present disclosure is A cell comprising a positive electrode, a negative electrode, and a diaphragm interposed between both electrodes, and used in a redox flow battery,
- the diaphragm includes an ion permeable portion having hydrogen ion permeability at least in the center when the diaphragm is viewed in plan view,
- the planar area of both the positive electrode and the negative electrode is 250 cm 2 or more, and the planar area of the ion permeable portion is smaller than the planar area of the positive electrode and the negative electrode,
- the planar area of the facing part that actually faces the positive electrode and the negative electrode in the ion permeable part is 50% or more and 99.9% of the smaller planar area of the positive electrode and the negative electrode. It is as follows.
- the cell stack of the present disclosure is A laminate in which a plurality of cells of the present disclosure are laminated; And a pair of end plates that sandwich the laminate from both sides in the lamination direction.
- the redox flow battery of the present disclosure is A cell stack of the present disclosure; A positive electrode circulation mechanism for circulating a positive electrode electrolyte in the cell; A negative electrode circulation mechanism for circulating a negative electrode electrolyte in the cell.
- the redox flow battery system of the present disclosure is A redox flow battery of the present disclosure; A detection device for detecting a power failure in the power system connected to the redox flow battery; And a control unit that operates the positive electrode circulation mechanism and the negative electrode circulation mechanism with the positive electrode electrolyte and the negative electrode electrolyte remaining in the cell based on the detection result of the detection device.
- FIG. 2 is an exploded view of a cell according to Embodiment 1.
- FIG. 2 is a longitudinal sectional view of a cell according to Embodiment 1.
- FIG. 2 is a longitudinal sectional view of a cell stack according to Embodiment 1.
- FIG. 1 is a schematic configuration diagram of a redox flow battery system including a redox flow battery according to Embodiment 1.
- FIG. 6 is an exploded view of a cell according to Embodiment 2.
- FIG. 6 is a longitudinal sectional view of a cell according to Embodiment 2.
- Patent Document 1 provides an uninterruptible power supply (UPS) that drives a circulation pump when a power failure occurs in an electric power system.
- UPS uninterruptible power supply
- an object of the present disclosure is to provide a cell and a cell stack capable of constructing a redox flow battery that can be discharged to the power system by itself when a power failure occurs in the power system.
- Another object of the present disclosure is to provide a redox flow battery and a redox flow battery system that can be discharged to the power system by itself when a power failure occurs in the power system.
- the cell according to the embodiment is A cell comprising a positive electrode, a negative electrode, and a diaphragm interposed between both electrodes, and used in a redox flow battery,
- the diaphragm includes an ion permeable portion having hydrogen ion permeability at least in the center when the diaphragm is viewed in plan view,
- the planar area of both the positive electrode and the negative electrode is 250 cm 2 or more, and the planar area of the ion permeable portion is smaller than the planar area of the positive electrode and the negative electrode,
- the planar area of the facing part that actually faces the positive electrode and the negative electrode in the ion permeable part is 50% or more and 99.9% of the smaller planar area of the positive electrode and the negative electrode. It is as follows.
- an emergency electrolyte solution can be stored in both electrodes, so that a redox flow battery that can be discharged to the power system by itself when a power failure occurs in the power system can be constructed.
- An emergency electrolyte can be stored in both electrodes because the planar area when both electrodes are viewed in plan is 250 cm 2 or more, and the planar area of the positive electrode, the negative electrode, and the opposing part of the ion permeable part of the diaphragm This is because the plane area of the facing portion is the smallest.
- planar area of the opposing part of the ion permeable part By making the planar area of the opposing part of the ion permeable part smaller than the planar area of both electrodes, a non-contact part where the ion permeable part does not contact is formed in both electrodes, and the battery reaction of the electrolyte in the non-contact part is performed. Can be suppressed.
- the electrolyte in which the battery reaction is suppressed can be used as an emergency electrolyte during a power failure.
- setting the planar area of both electrodes to 250 cm 2 or more, the amount of the electrolyte flowing through both electrodes increases, and a sufficient amount of the emergency electrolyte can be secured.
- planar area of the opposing part of the ion permeable part is 99.9% or less of the planar area of the smaller electrode, an amount of electrolyte sufficient for restarting the redox flow battery can be stored in each electrode.
- planar area of the ion permeable part is 50% or more of the planar area of the smaller electrode, it is possible to suppress the battery reaction area from becoming too small and the battery capacity of the redox flow battery from being excessively reduced.
- the planar area of the ion permeable part is further preferably 60% to 95%, more preferably 70% to 90% of the planar area of the smaller electrode.
- planar area of the diaphragm is smaller than both electrodes, an emergency electrolyte can be reliably ensured and the diaphragm material can be reduced.
- the planar area of the diaphragm is smaller than the planar areas of the positive electrode and the negative electrode, A first cell frame and a second cell frame having a bipolar plate and a frame, and sandwiching the diaphragm from one side and the other side thereof; A positive electrode space that is formed between the diaphragm and the bipolar plate of the first cell frame and houses the positive electrode; A negative electrode space that is formed between the diaphragm and the bipolar plate of the second cell frame and houses the negative electrode;
- sticker which has an inner peripheral part which touches over the perimeter of the outer periphery of the said diaphragm can be mentioned.
- the diaphragm includes the ion permeable portion and a frame-shaped ion non-permeable portion surrounding the outer periphery thereof, The form which the planar area of the said diaphragm is larger than any planar area of the said positive electrode and the said negative electrode can be mentioned.
- planar area of the diaphragm By making the planar area of the diaphragm larger than the planar area of both electrodes, contact between both electrodes can be effectively prevented.
- the material constituting the ion permeable part can be reduced by forming the diaphragm with the ion permeable part and the ion non-permeable part.
- the planar area of the diaphragm is larger than the planar area of both electrodes, A first cell frame and a second cell frame having a bipolar plate and a frame, and sandwiching the diaphragm from one side and the other side thereof; A positive electrode space that is formed between the diaphragm and the bipolar plate of the first cell frame and houses the positive electrode; A negative electrode space formed between the diaphragm and the bipolar plate of the second cell frame and containing the negative electrode; and
- connects the inner periphery of the said frame of the said 1st cell frame and the inner periphery of the said frame of the said 2nd cell frame can be mentioned.
- the gap of the diaphragm in the cell can be effectively suppressed by sandwiching the ion-impermeable portion of the diaphragm between the frame of the first cell frame and the frame of the second cell frame. Moreover, mixing of the positive electrode electrolyte and the negative electrode electrolyte in the cell can be suppressed by the diaphragm sandwiched between the frame bodies of both adjacent cell frames.
- the thickness of both the positive electrode and the negative electrode may be 0.1 mm or more and 4 mm or less.
- both electrodes By setting the thickness of both electrodes to 0.1 mm or more, a sufficient amount of the emergency electrolyte that can be stored in the electrodes can be secured. Moreover, it can suppress that the thickness of a cell becomes too thick because the thickness of both electrodes shall be 4 mm or less.
- the thickness is preferably 0.1 mm or more and 2.5 mm or less, and more preferably 0.1 mm or more and 1.5 mm or less.
- the cell stack according to the embodiment is A laminate in which a plurality of the cells according to the above ⁇ 1> to ⁇ 6> are laminated, And a pair of end plates that sandwich the laminate from both sides in the lamination direction.
- a redox flow battery that can be discharged to the power system by itself when the power system fails is provided. This is because, by forming a cell stack using the cells according to the embodiment, an emergency electrolyte can be stored in each of the plurality of cells in the cell stack.
- the redox flow battery according to the embodiment is ⁇ 7> cell stack above; A positive electrode circulation mechanism for circulating a positive electrode electrolyte in the cell; A negative electrode circulation mechanism for circulating a negative electrode electrolyte in the cell.
- the circulation pump provided in the positive and negative circulation mechanisms can be operated using the electric power of the electrolyte remaining in the cell. If the circulation pump can be operated, it is possible to take out the electric power of the electrolyte stored in the tank provided in the positive and negative circulation mechanisms, and the operation of the circulation pump can be further continued with the electric power. As a result, the power of the electrolytic solution in the tank can be discharged to the power system.
- the redox flow battery according to the embodiment can be discharged to the power system by itself.
- the redox flow battery system according to the embodiment is ⁇ 8> Redox flow battery, A detection device for detecting a power failure in the power system connected to the redox flow battery; And a control unit that operates the positive electrode circulation mechanism and the negative electrode circulation mechanism with the positive electrode electrolyte and the negative electrode electrolyte remaining in the cell based on the detection result of the detection device.
- the detection device and the control unit it is possible to automatically restart the redox flow battery when a power failure occurs in the power system, and to discharge the redox flow battery to the power system.
- the redox flow battery system of the embodiment that can be discharged by itself during a power failure of the power system does not require a UPS.
- UPS By not requiring UPS, for example, the following effects can be obtained.
- the battery capacity of the redox flow battery system can be improved by installing a large tank in the space used for the UPS installation space.
- the labor and cost of installing the UPS can be reduced.
- the RF battery is one of electrolyte circulation type storage batteries, and is used for storing new energy such as solar power generation and wind power generation.
- An RF battery is a battery that performs charging and discharging by utilizing the difference between the redox potential of active material ions contained in a positive electrode electrolyte and the redox potential of active material ions contained in a negative electrode electrolyte.
- the RF battery is connected to the substation equipment 90 of the power system 9 via the power converter 91, and performs charging / discharging with the power system 9.
- the power system 9 in this example is a power system that performs AC power transmission, and the power converter 91 is an AC / DC converter.
- the power system may be a power system that performs DC power transmission, in which case the power converter is a DC / DC converter.
- the RF battery includes a cell 100 separated into a positive electrode cell 102 and a negative electrode cell 103 by a diaphragm 101 that transmits hydrogen ions.
- a positive electrode 104 is built-in, and a positive electrolyte tank 106 for storing the positive electrolyte 8 ⁇ / b> P is connected via conduits 108 and 110.
- a circulation pump 112 is provided in the conduit 108, and a positive electrode circulation mechanism 100P that circulates the positive electrode electrolyte 8P is constituted by these members 106, 108, 110, and 112.
- a negative electrode electrode 105 is built in the negative electrode cell 103, and a negative electrode electrolyte tank 107 for storing the negative electrode electrolyte 8N is connected via conduits 109 and 111.
- a circulation pump 113 is provided in the conduit 109, and a negative electrode circulation mechanism 100N that circulates the negative electrode electrolyte 8N is constituted by these members 107, 109, 111, and 113.
- the electrolytes 8P and 8N stored in the tanks 106 and 107 are circulated in the cells 102 and 103 by the circulation pumps 112 and 113 at the time of charging and discharging. When charging / discharging is not performed, circulation pumps 112 and 113 are stopped, and electrolytes 8P and 8N are not circulated.
- the cell 1 of this example includes a first cell frame 2A and a second cell frame 2B that are adjacent to each other, and a positive electrode 104, a negative electrode 105, and a diaphragm 3 that are disposed between the two cell frames 2A and 2B.
- the cell 1 of this example further includes a pair of frame seals 4A and 4B.
- the first cell frame 2A and the second cell frame 2B are shown separated from each other, but the cell frames 2A and 2B are actually in close contact with each other.
- each configuration of the cell 1 will be described in detail.
- the first cell frame 2A and the second cell frame 2B are the same member, and include a frame body 22 having a through window and a bipolar plate 21 that closes the through window. That is, the frame 22 supports the bipolar plate 21 from the outer peripheral side.
- both the outer shape of the frame body 22 and the bipolar plate 21 provided in each cell frame 2A, 2B are rectangular, but they may be circular or polygonal.
- a sealing member 2s is sandwiched between the frame body 22 of the first cell frame 2A and the frame body 22 of the second cell frame 2B so that the electrolyte does not leak from the gap between the frame bodies 22. .
- the cell frames 2 ⁇ / b> A and 2 ⁇ / b> B can be manufactured, for example, by forming the frame body 22 integrally with the outer peripheral portion of the bipolar plate 21. Also, a frame body 22 in which the vicinity of the outer periphery of the through window is thinly formed and a bipolar plate 21 prepared separately from the frame body 22 are prepared, and the outer peripheral portion of the bipolar plate 21 is fitted into the thin portion of the frame body 22. Thus, the cell frames 2A and 2B can be manufactured. In this case, the bipolar plate 21 may be merely overlaid on the frame body 22 or may be bonded.
- the first cell frame 2A is formed with a positive electrode space 204 surrounded by one surface of the bipolar plate 21, the inner peripheral surface of the frame 22, and the diaphragm 3 described later.
- the positive electrode 104 is disposed at 204.
- the second cell frame 2B is formed with a negative electrode space 205 surrounded by the other surface of the bipolar plate 21, the inner peripheral surface of the frame 22, and the diaphragm 3 described later.
- 105 is arranged. In this configuration, one cell 1 is formed between the bipolar plates 21 fitted in the adjacent cell frames 2A and 2B.
- the positive electrode electrolyte is supplied from the liquid supply manifold 23 to the positive electrode 104 through an inlet slit 23s formed on one side (the front side of the paper) of the cell frames 2A and 2B, and is formed on the cell frames 2A and 2B. It is discharged to the drainage manifold 25 through the outlet slit 25s.
- the negative electrode electrolyte is supplied from the liquid supply manifold 24 to the negative electrode 105 via the inlet slit 24s formed on the other surface side (back side of the paper surface) of the cell frames 2A and 2B, and the cell frames 2A and 2B.
- the liquid is discharged to the drainage manifold 26 through an outlet slit 26s formed in the upper part.
- the bipolar plate 21 and the frame body 22 can be formed of a known material.
- the bipolar plate 21 may be formed of plastic carbon or the like
- the frame 22 may be formed of plastic such as vinyl chloride resin, polypropylene, polyethylene, fluorine resin, or epoxy resin.
- the positive electrode 104 is accommodated in the positive electrode space 204 of the first cell frame 2A, and the negative electrode 105 is accommodated in the negative electrode space 205 of the second cell frame 2B.
- the positive electrode 104 and the negative electrode 105 are disposed to face each other with the diaphragm 3 interposed therebetween.
- the positive electrode 104 and the negative electrode 105 in this example have substantially the same size and shape as the positive electrode space 204 and the negative electrode space 205, respectively.
- the positive electrode 104 and the negative electrode 105 may have different sizes and shapes.
- the thickness of the positive electrode 104 may be larger than the depth of the positive electrode space 204 (negative electrode space 205). In that case, when the cell 1 is assembled by tightening the cell frames 2A and 2B in the stacking direction (left and right direction in FIG. 2), the positive electrode 104 (negative electrode 105) is compressed and the positive electrode space 204 (negative electrode space 205). It will be in the state stored in.
- Both planar areas when the electrodes 104 and 105 are viewed in plan are set to 250 cm 2 or more.
- a sufficient amount of an emergency electrolyte for restarting the RF battery 10 can be stored in the cell 1. .
- the output of the RF battery can be increased by increasing the plane area.
- the plane area is preferably 300 cm 2 or more, and more preferably 400 cm 2 or more.
- the thickness of the positive electrode 104 (negative electrode 105) in the state accommodated in the positive electrode space 204 (negative electrode space 205) is preferably 0.1 mm or more and 4 mm or less.
- the thickness is preferably 0.1 mm or more and 2.5 mm or less, and more preferably 0.1 mm or more and 1.5 mm or less.
- the electrodes 104 and 105 can be formed of a known material, and are preferably formed of a porous material having elasticity.
- the electrodes 104 and 105 may be formed of carbon felt.
- the diaphragm 3 is interposed between the positive and negative electrodes 104 and 105 between the two cell frames 2A and 2B.
- the diaphragm 3 includes an ion permeable portion 30 at least on the center side when the diaphragm 3 is viewed in plan.
- the ion permeable portion 30 is a portion that allows hydrogen ions to pass therethrough but does not allow active material ions to pass therethrough.
- the entire surface of the diaphragm 3 of this example is constituted by the ion permeable portion 30.
- the diaphragm 3 of this example is formed in a size that does not reach the inner peripheral edge of the frame 22, and the planar area of the diaphragm 3, that is, the planar area of the ion permeable part 30 is smaller than the planar area of the electrodes 104 and 105. . Further, in the case of this example, since frame seals 4A and 4B, which will be described later, are interposed between the diaphragm 3 and the electrodes 104 and 105, of the ion permeable portion 30, the portion of the facing portion that actually faces the electrodes 104 and 105 is used. The planar area is smaller than the planar area of the entire ion permeable part 30.
- the planar area of the facing portion is 50% or more and 99.9% or less of the planar area of the smaller one of the electrodes 104 and 105.
- the planar area of the facing portion is preferably 60% or more and 95% or less of the planar area of the smaller electrode, and more preferably 70% or more and 90% or less. The significance of limiting the planar area of the facing portion will be described in detail in the column of effects in the subsequent stage.
- the diaphragm 3 can be formed of a known material.
- the diaphragm 3 may be formed of, for example, a sulfonated copolymer of styrene and divinylbenzene, a copolymer of perfluorosulfonic acid and polytetrafluoroethylene, or the like.
- the frame seals 4A and 4B are frame-shaped members disposed on the positive electrode 104 side and the negative electrode 105 side of the diaphragm 3, and seal positive and negative electrolyte solutions in the positive electrode space 204 and the negative electrode space 205, respectively.
- the frame seal 4A may be provided only on the positive electrode 104 side of the diaphragm 3, or the frame seal 4B may be provided only on the negative electrode 105 side of the diaphragm 3.
- the frame seals 4A and 4B have through-holes 40 (see particularly FIG. 2), the inner peripheral contour lines (contour lines of the through-holes 40) of the frame seals 4A and 4B are smaller than the diaphragm 3, and the outer peripheral contour lines are frame bodies.
- the frame seals 4A and 4B have an inner peripheral portion 41 that is in contact with the peripheral portion of the diaphragm 3 over the entire periphery, and an outer peripheral portion 42 that is sandwiched between the frame bodies 22 of both cell frames 2A and 2B without being in contact with the diaphragm 3. And functionally.
- the through holes of the frame seals 4A and 4B in the ion permeable portion 30 of the diaphragm 3 as shown in FIG. A portion where 40 is exposed is a facing portion that actually faces the electrodes 104 and 105. That is, in the case of this example, it can be said that the planar area of the facing portion of the ion permeable portion 30 is equal to the opening area of the through hole 40 of the frame seals 4A and 4B.
- each frame seal 4A, 4B is pressed by the repulsive force of each electrode 104, 105 when the cell 1 is assembled by tightening the cell frames 2A, 2B in the stacking direction (left and right direction in FIG. 2). Then, it is in close contact with the peripheral edge of the diaphragm 3.
- the outer peripheral portion 42 of each frame seal 4A, 4B is sandwiched between the frame bodies 22 and pressed into contact with the frame body 22 so as to be in close contact (contact). If the gaps between the frame bodies 22 and 22 of the cell frames 2A and 2B can be sealed by the frame seals 4A and 4B, the seal member 2s of FIG. 3 may be omitted.
- the frame seals 4A and 4B are in the form of a sheet or film, and the thickness is, for example, 0.1 mm or more and 2.0 mm or less, preferably 0.2 mm or more and 0.6 mm or less.
- the frame seals 4 ⁇ / b> A and 4 ⁇ / b> B have resistance to an electrolytic solution, and may be formed of a material that is cheaper and stronger than the diaphragm 3.
- the frame seals 4A and 4B may be formed of plastic or rubber such as vinyl chloride resin, polypropylene, polyethylene, fluorine resin, or epoxy resin.
- the inner periphery 41 of the frame seals 4A and 4B is brought into close contact with the peripheral edge of the diaphragm 3 by the repulsive force of the electrodes 104 and 105, thereby sealing between the inner periphery 41 of the frame seals 4A and 4B and the diaphragm 3. Can do. Further, since the outer peripheral portion 42 of the frame seals 4A and 4B is in close contact with the frame body 22, the space between the outer peripheral portion 42 of the frame seals 4A and 4B and the frame body 22 can be sealed.
- the frame seals 4A and 4B can suppress the leakage of the electrolytic solution from the spaces 204 and 205 and can suppress the mixing of the positive and negative electrolytic solutions while reducing the plane area of the diaphragm 3 as compared with the related art. Since the area of the diaphragm 3 can be small, the amount of the material for forming the diaphragm 3 can be reduced, and the cost can be reduced.
- an emergency electrolyte solution can be stored in both the electrodes 104 and 105. Therefore, a redox flow battery that can be discharged to the power system by itself during a power failure of the power system is provided. Can be built.
- the emergency electrolyte can be stored in both the electrodes 104 and 105 because the planar area when the electrodes 104 and 105 are viewed in plan is 250 cm 2 or more, and the planar area of the facing portion of the ion permeable portion 30 is both. This is because it is smaller than the plane area of the electrodes 104 and 105.
- the planar area of the opposing part of the ion permeable part 30 By making the planar area of the opposing part of the ion permeable part 30 smaller than the planar area of both the electrodes 104 and 105, a non-contact part where the ion permeable part 30 does not contact is formed in both the electrodes 104 and 105.
- the battery reaction of the electrolyte solution can be suppressed.
- the electrolyte in which the battery reaction is suppressed can be used as an emergency electrolyte during a power failure.
- the planar area of both the electrodes 104 and 105 to 250 cm 2 or more, the amount of the electrolyte flowing through both the electrodes 104 and 105 increases, and a sufficient amount of the emergency electrolyte can be secured.
- the cell 1 is usually formed inside a structure called a cell stack 5 as shown in FIG.
- the cell stack 5 is configured by sandwiching a laminated body 50 in which a plurality of sub-stacks 5 s are laminated between two end plates 52 and 52 and fastening them with a fastening mechanism 53.
- the sub-stack 5s has a configuration in which a plurality of cells 1 shown in FIGS. 2 and 3 are stacked and the stacked body is sandwiched between supply / discharge plates 51 and 51.
- a redox flow battery that can be discharged to the power system by itself when the power system fails is provided. This is because an emergency electrolyte can be stored in each of the plurality of cells 1 in the cell stack 5 by forming the cell stack 5 using the cells 1 shown in FIGS.
- the RF battery 10 includes a cell stack 5 shown in FIG. 4 and circulation mechanisms 100P and 100N connected to the cell stack 5.
- the configurations of the circulation mechanisms 100P and 100N are the same as the basic configuration described with reference to FIG. In FIG. 5, for convenience, the cell 1 is illustrated instead of the cell stack 5.
- 5 schematically shows the liquid level of the electrolytic solution 8 stored in the cell 1, but in the actual cell 1, the positive electrode electrolyte 8P and the negative electrode electrolyte 8N are not mixed.
- the RF battery system ⁇ of this example includes a charge / discharge control unit 6 that controls charge / discharge of the cell 1. More specifically, the charge / discharge control unit 6 controls the charge / discharge of the cell 1 by controlling the operation of the power converter 91 and the circulation pumps 112 and 113 by the signal line indicated by the thin line arrow.
- the power converter 91 controlled by the charge / discharge control unit 6 is a DC / AC converter if the power system 9 is AC, or a DC / DC converter if the power system 9 is DC.
- system 9 is connected to the charging / discharging control part 6.
- FIG. Therefore, the charge / discharge control part 6 can grasp
- the detection device 90 ⁇ / b> S a voltmeter that is provided in the substation equipment 90 and monitors the voltage of the power system 9 can be used.
- the charge / discharge control unit 6 is electrically connected to the power converter 91.
- the charging / discharging control unit 6 may be configured to be constantly supplied with power from the cell 1, or supplied with power from the power system 9 when the power system 9 is not powered down, and cell when the power system 9 is powered off. 1 may be configured to be supplied with electric power.
- a pump wiring 7 for supplying power from the power converter 91 to the circulation pumps 112 and 113 is provided.
- the pump wiring 7 may branch from between the power converter 91 and the power system 9 and extend to the circulation pumps 112 and 113.
- the circulation pumps 112 and 113 can be operated with power from the power system 9 when the power system 9 is not powered down, and the electrolyte 8 remaining in the cell 1 when the power system 9 is powered down.
- the circulation pumps 112 and 113 can be operated by using the electric power.
- the amount of power supplied to the circulation pumps 112 and 113 is controlled by the charge / discharge control unit 6.
- the operation signals of the circulation pumps 112 and 113 in this example are issued from the charge / discharge control unit 6 as indicated by thin line arrows.
- the operation signal is a signal for switching ON / OFF of the circulation pumps 112 and 113.
- the circulation pumps 112 and 113 of this example utilize what operates by alternating current. If the electric power system 9 is a direct current power transmission system, the circulation pumps 112 and 113 use what operates with direct current.
- electrolytes 8P and the negative electrode electrolyte 8N used in the RF battery 10 known electrolytes can be used.
- positive and negative electrolytes electrolytes containing V ions as positive and negative electrode active materials, Fe ions as positive electrode active materials, electrolytes containing Cr ions as negative electrode active materials, Mn ions as positive electrode active materials
- the negative electrode active material include an electrolytic solution containing Ti ions.
- the tanks 106 and 107 are disposed such that the liquid levels of the electrolytes 8P and 8N in the tanks 106 and 107 are higher than the liquid level of the electrolyte 8 in the cell 1. This is because the electrolytic solution 8 remains in the cell 1 when the circulation of the electrolytic solutions 8P and 8N is stopped.
- a valve may be provided in the conduits 108 and 109 so that the electrolytic solution 8 can be retained in the cell 1 even if the circulation of the electrolytic solutions 8P and 8N is stopped.
- the arrangement of the tanks 106 and 107 is not particularly limited.
- the circulation pumps 112 and 113 may be stopped to stop the circulation of the electrolytes 8P and 8N to the cell 1. Examples of the situation where the circulation pumps 112 and 113 are stopped include a case where the RF battery 10 is sufficiently charged.
- the charge / discharge control unit 6 of the RF battery system ⁇ operates the circulation pumps 112 and 113 using the power of the electrolyte 8 remaining in the cell 1 to The electric power of the electrolytes 8P and 8N is discharged to the power system 9.
- the cell 1 described with reference to FIGS. 2 and 3 is provided with an emergency electrolyte 8 in the cell 1 described with reference to FIGS. 2 and 3 so that sufficient electric power for operating the circulation pumps 112 and 113 can be taken out from the electrolyte 8 in the cell 1. It is because it becomes the structure which can be stored.
- the charging / discharging control part 6 detects the power failure of the electric power system 9 based on the change of the voltage of the electric power system 9 by the detection apparatus 90S.
- the charge / discharge control unit 6 restarts in a mode dedicated to the power failure.
- the power for restarting the charge / discharge control unit 6 is performed by the power of the electrolyte 8 remaining in the cell 1.
- the charge / discharge control unit 6 started in the mode dedicated for power failure instructs the power converter 91 to cause the power converter 91 to generate AC power having an optimum frequency for operating the circulation pumps 112 and 113. Then, the charge / discharge control unit 6 causes the power converter 91 to supply the alternating current to the circulation pumps 112 and 113 to operate the circulation pumps 112 and 113. Once the circulation pumps 112 and 113 are moved, the electrolytes 8P and 8N in the tanks 106 and 107 are sent to the cell 100, and the power of the electrolytes 8P and 8N can be taken out. Therefore, the operations of the circulation pumps 112 and 113 are continued. it can. As a result, the power of the electrolytes 8P and 8N in the tanks 106 and 107 can be discharged to the power system 9.
- the RF battery system ⁇ of the present example since the power system 9 can be discharged by itself upon a power failure, the RF battery system ⁇ does not require a UPS. By not requiring a UPS, the following effects can be obtained. [1] Since there is no need to secure an installation space for the UPS, the degree of freedom in installing the RF battery system ⁇ is high. [2] The battery capacity of the RF battery system ⁇ can be improved by installing large tanks 106 and 107 in the space used for the UPS installation space. [3] The labor and cost of installing the UPS can be reduced.
- the cell 1 of this example is implemented in that the frame seals 4A and 4B (FIGS. 2 and 3) are not used and the diaphragm 3 is larger than the electrodes 104 and 105. Different from the cell 1 of the form 1.
- the diaphragm 3 includes an ion permeable part 30 and an ion non-permeable part 31 surrounding the outer periphery thereof.
- a diaphragm 3 is obtained, for example, by preparing a base material that does not transmit hydrogen ions and post-processing the central portion of the base material.
- the post-processed part of the base material becomes the ion permeable part 30, and the other part becomes the ion non-permeable part 31.
- Examples of the post-treatment include application and impregnation of an ion exchange resin, and impregnation and sintering of a polymer alcohol.
- the planar area of the ion permeable part 30 of the diaphragm 3 is smaller than the planar area of the electrodes 104 and 105, and the planar area of the entire diaphragm 3 is larger than the planar area of the through window of the frame 22.
- the ion-impermeable portion 31 of the diaphragm 3 is separated from the inner periphery of the frame 22 of the first cell frame 2A and the inner periphery of the frame 22 of the second cell frame 2B. To touch.
- the ion-impermeable portion 31 further has a size that extends to the seal member 2s, so that positive and negative electrolytes can be easily sealed in the positive electrode space 204 and the negative electrode space 205, respectively, and electrolysis can be performed outside the cell 1. Liquid does not leak easily.
- the entire surface of the ion permeable portion 30 is a facing portion that faces the electrodes 104 and 105. That is, the planar area of the facing portion is the planar area of the ion permeable portion 30.
- the electrolysis for emergency use in the cell 1 as in the cell 1 of the first embodiment. Liquid can be stored. Therefore, if the RF battery system ⁇ shown in FIG. 5 is constructed using the cell 1 of this example, the RF battery system ⁇ can discharge the power system 9 by itself when the power system 9 is powered off.
- the RF battery system ⁇ of the embodiment is a storage battery for the purpose of stabilizing fluctuations in power generation output, power storage when surplus generated power, load leveling, etc., for power generation of new energy such as solar power generation and wind power generation Available as a system.
- the RF battery system ⁇ according to the present embodiment can be used as a large-capacity storage battery system that is provided in a general power plant and is intended for measures against instantaneous voltage drop, power failure, and load leveling.
- test body cells A to D in which the planar area of the diaphragm 3 in the cell 1 of the first embodiment is changed, and the RF battery system ⁇ in FIG. 5 is used with the electrolyte remaining in the test body cells A to D. It was tested whether the circulating pumps 112 and 113 could be started.
- the electrodes 104 and 105 used for each of the test body cells A to D were common, and the planar area of the electrodes 104 and 105 was 250 cm 2 and the thickness was 1 mm.
- Specimen cell A Cell 1 in which the planar area of the facing portion facing the electrodes 104 and 105 in the ion permeable portion 30 is 99.9% of the planar area of the electrodes 104 and 105
- Specimen cell B Cell 1 in which the planar area of the facing portion is 75% of the planar area of the electrodes 104 and 105
- Specimen cell C Cell 1 in which the planar area of the opposing portion is 99.95% of the planar area of the electrodes 104 and 105
- Specimen cell D Cell 1 in which the planar area of the facing portion is the same as the planar area of the electrodes 104 and 105
- test body cells A and B could start the circulation pumps 112 and 113, but the test body cells C and D could not start the circulation pumps 112 and 113. From these results, in order to store an emergency electrolyte enough to activate the circulation pumps 112 and 113 in the cell 1, at least the plane area of the opposing portion of the ion permeable portion 30 is equal to the plane area of the electrodes 104 and 105. It turned out that it is necessary to make it 99.9% or less.
- Redox flow battery system 10 Redox flow battery (RF battery) 1 cell 2A first cell frame 2B second cell frame 2s seal member 21 bipolar plate 22 frame body 23, 24 manifold for liquid supply 25, 26 manifold for liquid discharge 23s, 24s inlet slit 25s, 26s outlet slit 204 positive electrode space 205 negative electrode Space 3 Diaphragm 30 Ion permeation part 31 Ion non-permeation part 4A, 4B Frame seal 40 Through hole 41 Inner peripheral part 42 Outer peripheral part 5 Cell stack 5s Sub stack 50 Laminated body 51 Supply / discharge plate 52 End plate 53 Tightening mechanism 6 Charging / discharging Control unit (control unit) 7 Pump wiring 8 Electrolyte 8P Cathode electrolyte 8N Anode electrolyte 9 Power system 90 Substation equipment 91 Power converter 90S Detector 100 Cell 101 Separator 102 Cathode cell 103 Negative electrode 100P Cathode circulation mechanism 100N Cathode circulation mechanism 104 Cathode electrode 105
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Abstract
Description
正極電極と負極電極と両電極の間に介在される隔膜とを備え、レドックスフロー電池に用いられるセルであって、
前記隔膜は、前記隔膜を平面視したときの少なくとも中央側に、水素イオン透過能を有するイオン透過部を備え、
前記正極電極及び前記負極電極の平面面積が共に250cm2以上で、かつ前記イオン透過部の平面面積が、前記正極電極及び前記負極電極の平面面積よりも小さく、
更に前記イオン透過部のうち、実際に前記正極電極及び前記負極電極に対向する対向部の平面面積は、前記正極電極及び前記負極電極のうちの小さい方の平面面積の50%以上99.9%以下である。 The cell of the present disclosure is
A cell comprising a positive electrode, a negative electrode, and a diaphragm interposed between both electrodes, and used in a redox flow battery,
The diaphragm includes an ion permeable portion having hydrogen ion permeability at least in the center when the diaphragm is viewed in plan view,
The planar area of both the positive electrode and the negative electrode is 250 cm 2 or more, and the planar area of the ion permeable portion is smaller than the planar area of the positive electrode and the negative electrode,
Furthermore, the planar area of the facing part that actually faces the positive electrode and the negative electrode in the ion permeable part is 50% or more and 99.9% of the smaller planar area of the positive electrode and the negative electrode. It is as follows.
本開示のセルを複数積層した積層体と、
前記積層体をその積層方向の両側から挟み込む一対のエンドプレートと、を備える。 The cell stack of the present disclosure is
A laminate in which a plurality of cells of the present disclosure are laminated;
And a pair of end plates that sandwich the laminate from both sides in the lamination direction.
本開示のセルスタックと、
前記セルに正極電解液を循環させる正極循環機構と、
前記セルに負極電解液を循環させる負極循環機構と、を備える。 The redox flow battery of the present disclosure is
A cell stack of the present disclosure;
A positive electrode circulation mechanism for circulating a positive electrode electrolyte in the cell;
A negative electrode circulation mechanism for circulating a negative electrode electrolyte in the cell.
本開示のレドックスフロー電池と、
前記レドックスフロー電池に繋がる電力系統の停電を検知する検知装置と、
前記検知装置の検知結果に基づいて、前記セル内に残存する前記正極電解液と前記負極電解液とで、前記正極循環機構及び前記負極循環機構を動作させる制御部と、を備える。 The redox flow battery system of the present disclosure is
A redox flow battery of the present disclosure;
A detection device for detecting a power failure in the power system connected to the redox flow battery;
And a control unit that operates the positive electrode circulation mechanism and the negative electrode circulation mechanism with the positive electrode electrolyte and the negative electrode electrolyte remaining in the cell based on the detection result of the detection device.
レドックスフロー電池システムは、電力系統の停電時に自力で電力系統に放電できない。レドックスフロー電池システムでは、セル内に電解液を循環させる循環ポンプが停止すると、継続的に充放電できないからである。その対策として、特許文献1では、電力系統の停電時に循環ポンプを駆動する無停電電源装置(Uninterruptible Power Supply:UPS)が設けられている。しかし、循環ポンプを動作させる電力をまかなうためのUPSはレドックスフロー電池の電池容量に応じて大型化するため、設置スペースを多く必要とするという問題や、設置コストがかかるという問題がある。 [Problems to be solved by the present disclosure]
The redox flow battery system cannot discharge to the power system by itself when the power system fails. This is because in the redox flow battery system, when the circulation pump that circulates the electrolyte in the cell is stopped, charging and discharging cannot be performed continuously. As a countermeasure,
最初に本願発明の実施形態の内容を列記して説明する。 [Description of Embodiment of Present Invention]
First, the contents of the embodiments of the present invention will be listed and described.
正極電極と負極電極と両電極の間に介在される隔膜とを備え、レドックスフロー電池に用いられるセルであって、
前記隔膜は、前記隔膜を平面視したときの少なくとも中央側に、水素イオン透過能を有するイオン透過部を備え、
前記正極電極及び前記負極電極の平面面積が共に250cm2以上で、かつ前記イオン透過部の平面面積が、前記正極電極及び前記負極電極の平面面積よりも小さく、
更に前記イオン透過部のうち、実際に前記正極電極及び前記負極電極に対向する対向部の平面面積は、前記正極電極及び前記負極電極のうちの小さい方の平面面積の50%以上99.9%以下である。 <1> The cell according to the embodiment is
A cell comprising a positive electrode, a negative electrode, and a diaphragm interposed between both electrodes, and used in a redox flow battery,
The diaphragm includes an ion permeable portion having hydrogen ion permeability at least in the center when the diaphragm is viewed in plan view,
The planar area of both the positive electrode and the negative electrode is 250 cm 2 or more, and the planar area of the ion permeable portion is smaller than the planar area of the positive electrode and the negative electrode,
Furthermore, the planar area of the facing part that actually faces the positive electrode and the negative electrode in the ion permeable part is 50% or more and 99.9% of the smaller planar area of the positive electrode and the negative electrode. It is as follows.
前記隔膜の平面面積が、前記正極電極及び前記負極電極の平面面積よりも小さい形態を挙げることができる。 <2> As one mode of the cell according to the embodiment,
A mode in which the planar area of the diaphragm is smaller than the planar areas of the positive electrode and the negative electrode can be mentioned.
双極板と枠体とを有し、前記隔膜をその一面側と他面側から挟み込む第一セルフレーム及び第二セルフレームと、
前記隔膜と、前記第一セルフレームの前記双極板と、の間に形成され、前記正極電極を収納する正極空間と、
前記隔膜と、前記第二セルフレームの前記双極板と、の間に形成され、前記負極電極を収納する負極空間と、
前記隔膜に接することなく前記枠体の内周縁の全周にわたって接する外周部、及び前記隔膜の外周縁の全周にわたって接する内周部を有する枠シールと、を備える形態を挙げることができる。 <3> As one form of the cell according to the embodiment, the planar area of the diaphragm is smaller than the planar areas of the positive electrode and the negative electrode,
A first cell frame and a second cell frame having a bipolar plate and a frame, and sandwiching the diaphragm from one side and the other side thereof;
A positive electrode space that is formed between the diaphragm and the bipolar plate of the first cell frame and houses the positive electrode;
A negative electrode space that is formed between the diaphragm and the bipolar plate of the second cell frame and houses the negative electrode;
The form provided with the outer peripheral part which touches the perimeter of the inner periphery of the said frame body without contacting the said diaphragm, and the frame seal | sticker which has an inner peripheral part which touches over the perimeter of the outer periphery of the said diaphragm can be mentioned.
前記隔膜は、前記イオン透過部と、その外周を取り囲む枠状のイオン非透過部と、を備え、
前記隔膜の平面面積が、前記正極電極と前記負極電極のいずれの平面面積よりも大きい形態を挙げることができる。 <4> As one mode of the cell according to the embodiment,
The diaphragm includes the ion permeable portion and a frame-shaped ion non-permeable portion surrounding the outer periphery thereof,
The form which the planar area of the said diaphragm is larger than any planar area of the said positive electrode and the said negative electrode can be mentioned.
双極板と枠体とを有し、前記隔膜をその一面側と他面側から挟み込む第一セルフレーム及び第二セルフレームと、
前記隔膜と、前記第一セルフレームの前記双極板と、の間に形成され、前記正極電極を収納する正極空間と、
前記隔膜と、前記第二セルフレームの前記双極板と、の間に形成され、前記負極電極を収納する負極空間と、を備え、
前記隔膜の前記イオン非透過部が、前記第一セルフレームの前記枠体の内周縁と、前記第二セルフレームの前記枠体の内周縁とに接する形態を挙げることができる。 <5> As one form of the cell according to the embodiment, the planar area of the diaphragm is larger than the planar area of both electrodes,
A first cell frame and a second cell frame having a bipolar plate and a frame, and sandwiching the diaphragm from one side and the other side thereof;
A positive electrode space that is formed between the diaphragm and the bipolar plate of the first cell frame and houses the positive electrode;
A negative electrode space formed between the diaphragm and the bipolar plate of the second cell frame and containing the negative electrode; and
The form which the said ion impermeable part of the said diaphragm contact | connects the inner periphery of the said frame of the said 1st cell frame and the inner periphery of the said frame of the said 2nd cell frame can be mentioned.
前記正極電極と前記負極電極の厚さは共に、0.1mm以上4mm以下である形態を挙げることができる。 <6> As one mode of the cell according to the embodiment,
The thickness of both the positive electrode and the negative electrode may be 0.1 mm or more and 4 mm or less.
上記<1>から<6>のいずれかのセルを複数積層した積層体と、
前記積層体をその積層方向の両側から挟み込む一対のエンドプレートと、を備える。 <7> The cell stack according to the embodiment is
A laminate in which a plurality of the cells according to the above <1> to <6> are laminated,
And a pair of end plates that sandwich the laminate from both sides in the lamination direction.
上記<7>のセルスタックと、
前記セルに正極電解液を循環させる正極循環機構と、
前記セルに負極電解液を循環させる負極循環機構と、を備える。 <8> The redox flow battery according to the embodiment is
<7> cell stack above;
A positive electrode circulation mechanism for circulating a positive electrode electrolyte in the cell;
A negative electrode circulation mechanism for circulating a negative electrode electrolyte in the cell.
上記<8>のレドックスフロー電池と、
前記レドックスフロー電池に繋がる電力系統の停電を検知する検知装置と、
前記検知装置の検知結果に基づいて、前記セル内に残存する前記正極電解液と前記負極電解液とで、前記正極循環機構及び前記負極循環機構を動作させる制御部と、を備える。 <9> The redox flow battery system according to the embodiment is
<8> Redox flow battery,
A detection device for detecting a power failure in the power system connected to the redox flow battery;
And a control unit that operates the positive electrode circulation mechanism and the negative electrode circulation mechanism with the positive electrode electrolyte and the negative electrode electrolyte remaining in the cell based on the detection result of the detection device.
[1]UPSの設置スペースを確保する必要がないため、レドックスフロー電池システムの設置場所の自由度が高い。
[2]UPSの設置スペースに利用していた空間により大型のタンクを設置するなどして、レドックスフロー電池システムの電池容量の向上を図ることができる。
[3]UPSの設置の手間、コストを削減することができる。 The redox flow battery system of the embodiment that can be discharged by itself during a power failure of the power system does not require a UPS. By not requiring UPS, for example, the following effects can be obtained.
[1] Since it is not necessary to secure a space for installing the UPS, the degree of freedom in installing the redox flow battery system is high.
[2] The battery capacity of the redox flow battery system can be improved by installing a large tank in the space used for the UPS installation space.
[3] The labor and cost of installing the UPS can be reduced.
以下、本開示のセル、セルスタック、レドックスフロー電池、及びレドックスフロー電池システムの実施形態を説明する。なお、本願発明は実施形態に示される構成に限定されるわけではなく、請求の範囲によって示され、請求の範囲と均等の意味および範囲内の全ての変更が含まれることを意図する。 [Details of the embodiment of the present invention]
Hereinafter, embodiments of the cell, the cell stack, the redox flow battery, and the redox flow battery system of the present disclosure will be described. Note that the present invention is not limited to the configuration shown in the embodiment, but is shown by the scope of claims and is intended to include meanings equivalent to the scope of claims and all modifications within the scope.
実施形態に係るセル、セルスタック、レドックスフロー電池、及びレドックスフロー電池システムの説明に先立ち、レドックスフロー電池(以下、RF電池)の基本構成を図1に基づいて説明する。 <
Prior to the description of the cell, the cell stack, the redox flow battery, and the redox flow battery system according to the embodiment, the basic configuration of the redox flow battery (hereinafter referred to as RF battery) will be described with reference to FIG.
RF電池は、電解液循環型の蓄電池の一つであって、太陽光発電や風力発電といった新エネルギーの蓄電などに利用されている。このRF電池の動作原理を図1に基づいて説明する。RF電池は、正極電解液に含まれる活物質イオンの酸化還元電位と、負極電解液に含まれる活物質イオンの酸化還元電位との差を利用して充放電を行う電池である。RF電池は、電力変換器91を介して、電力系統9の変電設備90に繋がっており、電力系統9との間で充放電を行なう。本例の電力系統9は交流送電を行う電力系統であって、電力変換器91は交流/直流変換器である。電力系統は直流送電を行う電力系統であっても良く、その場合、電力変換器は直流/直流変換器である。一方、RF電池は、水素イオンを透過させる隔膜101で正極セル102と負極セル103とに分離されたセル100を備える。 ≪Basic structure≫
The RF battery is one of electrolyte circulation type storage batteries, and is used for storing new energy such as solar power generation and wind power generation. The operation principle of this RF battery will be described with reference to FIG. An RF battery is a battery that performs charging and discharging by utilizing the difference between the redox potential of active material ions contained in a positive electrode electrolyte and the redox potential of active material ions contained in a negative electrode electrolyte. The RF battery is connected to the
以上説明したRF電池の基本構成を踏まえて、実施形態に係るセル1を図2,3に基づいて説明する。本例のセル1は、互いに隣接する第一セルフレーム2A及び第二セルフレーム2Bと、両セルフレーム2A,2B間に配置される正極電極104、負極電極105、及び隔膜3を備える。本例のセル1は更に、一対の枠シール4A,4Bを備える。ここで、図3では第一セルフレーム2Aと第二セルフレーム2Bとを離隔した状態で示しているが、実際にはセルフレーム2A,2Bはほぼ密着している。以下、セル1の各構成を詳細に説明する。 ≪Cell≫
Based on the basic configuration of the RF battery described above, the
第一セルフレーム2Aと第二セルフレーム2Bとは、同じ部材であり、貫通窓を有する枠体22と、貫通窓を塞ぐ双極板21と、を有している。つまり、枠体22は、双極板21をその外周側から支持している。本例では、各セルフレーム2A,2Bに備わる枠体22の外形も双極板21の形状も矩形状であるが、円形状や多角形状などであってもかまわない。第一セルフレーム2Aの枠体22と第二セルフレーム2Bの枠体22との間にはシール部材2sが挟み込まれており、枠体22同士の隙間から電解液が漏れないようになっている。 [Cell frame]
The
図3に示すように、正極電極104は、第一セルフレーム2Aの正極空間204に収納され、負極電極105は、第二セルフレーム2Bの負極空間205に収納される。正極電極104と負極電極105とは隔膜3を挟んで互いに対向して配置される。本例の正極電極104及び負極電極105はそれぞれ、正極空間204及び負極空間205と略同じサイズ・同じ形状である。正極電極104と負極電極105とはサイズや形状が異なっていてもかまわない。 [electrode]
As shown in FIG. 3, the
隔膜3は、両セルフレーム2A,2B間で正負の電極104,105間に介在される。隔膜3は、隔膜3を平面視したときの少なくとも中央側にイオン透過部30を備える。イオン透過部30は水素イオンを透過させるが、活物質イオンは透過させない部分であって、本例の隔膜3はその全面がイオン透過部30で構成されている。 [diaphragm]
The
枠シール4A,4Bは、隔膜3の正極電極104側及び負極電極105側に配置される枠状の部材であって、正負の電解液をそれぞれ正極空間204及び負極空間205内に封止する。隔膜3の正極電極104側にのみ枠シール4Aを設けても良いし、隔膜3の負極電極105側にのみ枠シール4Bを設けても良い。枠シール4A,4Bは貫通孔40(特に図2参照)を有し、枠シール4A,4Bの内周輪郭線(貫通孔40の輪郭線)は隔膜3よりも小さく、外周輪郭線は枠体22の内周輪郭線よりも小さい。そのため、枠シール4A,4Bは、隔膜3の周縁部に全周に亘って接する内周部41と、隔膜3に接することなく両セルフレーム2A,2Bの枠体22間に挟まれる外周部42と、に機能上区分することができる。 [Frame seal]
The frame seals 4A and 4B are frame-shaped members disposed on the
以上説明した構成を備えるセル1によれば、両電極104,105内に非常用の電解液を貯留しておくことができるので、電力系統の停電時に自力で電力系統に放電できるレドックスフロー電池を構築することができる。両電極104,105内に非常用の電解液を貯留できるのは、両電極104,105を平面視したときの平面面積が250cm2以上で、かつイオン透過部30の対向部の平面面積が両電極104,105の平面面積よりも小さくなっているからである。イオン透過部30の対向部の平面面積を両電極104,105の平面面積よりも小さくすることで、両電極104,105においてイオン透過部30が接触しない非接触部分が形成され、当該非接触部分にある電解液の電池反応を抑制できる。この電池反応が抑制された電解液が、停電時に非常用の電解液として利用できる。ここで、両電極104,105の平面面積を250cm2以上とすることで、両電極104,105に流通される電解液量が多くなり、非常用の電解液が十分な量確保できる。 [effect]
According to the
上記セル1は通常、図4に示すような、セルスタック5と呼ばれる構造体の内部に形成される。セルスタック5はサブスタック5sを複数積層した積層体50を二枚のエンドプレート52,52で挟み込み、締付機構53で締め付けることで構成されている。サブスタック5sは、図2,3に示すセル1を複数積層し、その積層体を給排板51,51で挟み込んだ構成を備える。 ≪Cell stack≫
The
図5を参照して、RF電池10と、そのRF電池10を備えるRF電池システムαを説明する。RF電池10は、図4に示すセルスタック5と、セルスタック5に繋がる循環機構100P,100Nと、を備える。循環機構100P,100Nの構成は、図1を参照して説明した基本構成と同じである。図5では便宜上、セルスタック5の代わりにセル1を図示している。また、図5ではセル1内に貯留される電解液8の液面を模式的に示しているが、実際のセル1内では、正極電解液8Pと負極電解液8Nとは混合されない。 ≪RF battery and RF battery system≫
With reference to FIG. 5, the
本例のRF電池システムαは、セル1の充放電を制御する充放電制御部6を備える。より具体的には、充放電制御部6は、細線矢印で示す信号線によって、電力変換器91と循環ポンプ112,113の動作を制御することで、セル1の充放電を制御する。充放電制御部6で制御する電力変換器91は、電力系統9が交流であれば直流/交流変換器、直流であれば直流/直流変換器などである。 [Charge / Discharge Control Unit]
The RF battery system α of this example includes a charge /
RF電池10に用いる正極電解液8Pと負極電解液8Nには、公知の電解液を使用できる。例えば、正負の電解液としては、正極及び負極の活物質としてVイオンを含有する電解液、正極活物質としてFeイオン、負極活物質としてCrイオンを含有する電解液、正極活物質としてMnイオン、負極活物質としてTiイオンを含有する電解液などが挙げられる。 [Electrolyte]
As the
[通常運転時]
RF電池システムαの通常運転時(非停電時)、RF電池システムαの充放電制御部6は、電力変換器91と循環ポンプ112,113の動作を制御してセル1の充放電を制御する。 ≪Operation method of RF battery system≫
[During normal operation]
During normal operation of the RF battery system α (when there is no power failure), the charge /
電力系統9の停電時、RF電池システムαの充放電制御部6は、セル1内に残存する電解液8の電力を利用して、循環ポンプ112,113を動作させ、タンク106,107内の電解液8P,8Nの電力を電力系統9に放電する。循環ポンプ112,113を動作させるのに十分な電力をセル1内の電解液8から取り出せるのは、図2,3を参照して説明したセル1が、その内部に非常用の電解液8を貯留できる構成となっているからである。 [In case of power failure in power system]
At the time of a power failure of the
上述したように、本例のRF電池システムαによれば、電力系統9の停電時に自力で放電できるため、RF電池システムαにUPSを必要としない。UPSを必要としないことで、次のような効果を得ることができる。
[1]UPSの設置スペースを確保する必要がないため、RF電池システムαの設置場所の自由度が高い。
[2]UPSの設置スペースに利用していた空間により大型のタンク106,107を設置するなどして、RF電池システムαの電池容量の向上を図ることができる。
[3]UPSの設置の手間、コストを削減することができる。 [effect]
As described above, according to the RF battery system α of the present example, since the
[1] Since there is no need to secure an installation space for the UPS, the degree of freedom in installing the RF battery system α is high.
[2] The battery capacity of the RF battery system α can be improved by installing
[3] The labor and cost of installing the UPS can be reduced.
実施形態2では、実施形態1とは異なるセル1を図6,7に基づいて説明する。 <
In the second embodiment, a
実施形態のRF電池システムαは、太陽光発電、風力発電などの新エネルギーの発電に対して、発電出力の変動の安定化、発電電力の余剰時の蓄電、負荷平準化などを目的とした蓄電池システムとして利用できる。また、本実施形態のRF電池システムαは、一般的な発電所に併設されて、瞬低・停電対策や負荷平準化を目的とした大容量の蓄電池システムとしても利用することができる。 <Application>
The RF battery system α of the embodiment is a storage battery for the purpose of stabilizing fluctuations in power generation output, power storage when surplus generated power, load leveling, etc., for power generation of new energy such as solar power generation and wind power generation Available as a system. In addition, the RF battery system α according to the present embodiment can be used as a large-capacity storage battery system that is provided in a general power plant and is intended for measures against instantaneous voltage drop, power failure, and load leveling.
試験例では、実施形態1のセル1における隔膜3の平面面積を変化させた試験体セルA~Dを作製し、試験体セルA~D内に残存する電解液で図5のRF電池システムαの循環ポンプ112,113を起動させることができるかを試験した。各試験体セルA~Dに用いる電極104,105は共通で、電極104,105の平面面積は250cm2、厚さは1mmであった。 <Test example>
In the test example, test body cells A to D in which the planar area of the
・試験体セルB…対向部の平面面積を電極104,105の平面面積の75%としたセル1
・試験体セルC…対向部の平面面積を電極104,105の平面面積の99.95%としたセル1
・試験体セルD…対向部の平面面積が電極104,105の平面面積と同じとしたセル1 Specimen cell A:
Specimen cell B:
Specimen cell C:
Specimen cell D:
10 レドックスフロー電池(RF電池)
1 セル
2A 第一セルフレーム 2B 第二セルフレーム 2s シール部材
21 双極板 22 枠体
23,24 給液用マニホールド 25,26 排液用マニホールド
23s,24s 入口スリット 25s,26s 出口スリット
204 正極空間 205 負極空間
3 隔膜
30 イオン透過部 31 イオン非透過部
4A,4B 枠シール
40 貫通孔 41 内周部 42 外周部
5 セルスタック 5s サブスタック
50 積層体 51 給排板 52 エンドプレート 53 締付機構
6 充放電制御部(制御部)
7 ポンプ配線
8 電解液 8P 正極電解液 8N 負極電解液
9 電力系統
90 変電設備 91 電力変換器 90S 検知装置
100 セル 101 隔膜 102 正極セル 103 負極セル
100P 正極用循環機構 100N 負極用循環機構
104 正極電極 105 負極電極 106 正極電解液用タンク
107 負極電解液用タンク 108,109,110,111 導管
112,113 循環ポンプ α Redox flow battery system (RF battery system)
10 Redox flow battery (RF battery)
1
7
Claims (9)
- 正極電極と負極電極と両電極の間に介在される隔膜とを備え、レドックスフロー電池に用いられるセルであって、
前記隔膜は、前記隔膜を平面視したときの少なくとも中央側に、水素イオン透過能を有するイオン透過部を備え、
前記正極電極及び前記負極電極の平面面積が共に250cm2以上で、かつ前記イオン透過部の平面面積が、前記正極電極及び前記負極電極の平面面積よりも小さく、
更に前記イオン透過部のうち、実際に前記正極電極及び前記負極電極に対向する対向部の平面面積は、前記正極電極及び前記負極電極のうちの小さい方の平面面積の50%以上99.9%以下であるセル。 A cell comprising a positive electrode, a negative electrode, and a diaphragm interposed between both electrodes, and used in a redox flow battery,
The diaphragm includes an ion permeable portion having hydrogen ion permeability at least in the center when the diaphragm is viewed in plan view,
The planar area of both the positive electrode and the negative electrode is 250 cm 2 or more, and the planar area of the ion permeable portion is smaller than the planar area of the positive electrode and the negative electrode,
Furthermore, the planar area of the facing part that actually faces the positive electrode and the negative electrode in the ion permeable part is 50% or more and 99.9% of the smaller planar area of the positive electrode and the negative electrode. A cell that is: - 前記隔膜の平面面積が、前記正極電極及び前記負極電極の平面面積よりも小さい請求項1に記載のセル。 The cell according to claim 1, wherein the planar area of the diaphragm is smaller than the planar areas of the positive electrode and the negative electrode.
- 双極板と枠体とを有し、前記隔膜をその一面側と他面側から挟み込む第一セルフレーム及び第二セルフレームと、
前記隔膜と、前記第一セルフレームの前記双極板と、の間に形成され、前記正極電極を収納する正極空間と、
前記隔膜と、前記第二セルフレームの前記双極板と、の間に形成され、前記負極電極を収納する負極空間と、
前記隔膜に接することなく前記枠体の内周縁の全周にわたって接する外周部、及び前記隔膜の外周縁の全周にわたって接する内周部を有する枠シールと、を備える請求項2に記載のセル。 A first cell frame and a second cell frame having a bipolar plate and a frame, and sandwiching the diaphragm from one side and the other side thereof;
A positive electrode space that is formed between the diaphragm and the bipolar plate of the first cell frame and houses the positive electrode;
A negative electrode space that is formed between the diaphragm and the bipolar plate of the second cell frame and houses the negative electrode;
The cell according to claim 2, further comprising: an outer peripheral portion that is in contact with the entire inner periphery of the frame body without contacting the diaphragm, and a frame seal having an inner peripheral portion that is in contact with the entire outer periphery of the diaphragm. - 前記隔膜は、前記イオン透過部と、その外周を取り囲む枠状のイオン非透過部と、を備え、
前記隔膜の平面面積が、前記正極電極と前記負極電極のいずれの平面面積よりも大きい請求項1に記載のセル。 The diaphragm includes the ion permeable portion and a frame-shaped ion non-permeable portion surrounding the outer periphery thereof,
The cell according to claim 1, wherein a planar area of the diaphragm is larger than a planar area of either the positive electrode or the negative electrode. - 双極板と枠体とを有し、前記隔膜をその一面側と他面側から挟み込む第一セルフレーム及び第二セルフレームと、
前記隔膜と、前記第一セルフレームの前記双極板と、の間に形成され、前記正極電極を収納する正極空間と、
前記隔膜と、前記第二セルフレームの前記双極板と、の間に形成され、前記負極電極を収納する負極空間と、を備え、
前記隔膜の前記イオン非透過部が、前記第一セルフレームの前記枠体の内周縁と、前記第二セルフレームの前記枠体の内周縁とに接する請求項4に記載のセル。 A first cell frame and a second cell frame having a bipolar plate and a frame, and sandwiching the diaphragm from one side and the other side thereof;
A positive electrode space that is formed between the diaphragm and the bipolar plate of the first cell frame and houses the positive electrode;
A negative electrode space formed between the diaphragm and the bipolar plate of the second cell frame and containing the negative electrode; and
The cell according to claim 4, wherein the ion-impermeable portion of the diaphragm is in contact with an inner peripheral edge of the frame body of the first cell frame and an inner peripheral edge of the frame body of the second cell frame. - 前記正極電極と前記負極電極の厚さは共に、0.1mm以上4mm以下である請求項1から請求項5のいずれか1項に記載のセル。 The cell according to any one of claims 1 to 5, wherein a thickness of each of the positive electrode and the negative electrode is 0.1 mm or more and 4 mm or less.
- 請求項1から請求項6のいずれか1項に記載のセルを複数積層した積層体と、
前記積層体をその積層方向の両側から挟み込む一対のエンドプレートと、を備えるセルスタック。 A laminate in which a plurality of the cells according to any one of claims 1 to 6 are laminated,
A cell stack comprising: a pair of end plates that sandwich the stacked body from both sides in the stacking direction. - 請求項7のセルスタックと、
前記セルに正極電解液を循環させる正極循環機構と、
前記セルに負極電解液を循環させる負極循環機構と、を備えるレドックスフロー電池。 The cell stack of claim 7;
A positive electrode circulation mechanism for circulating a positive electrode electrolyte in the cell;
A redox flow battery comprising: a negative electrode circulation mechanism that circulates a negative electrode electrolyte in the cell. - 請求項8に記載のレドックスフロー電池と、
前記レドックスフロー電池に繋がる電力系統の停電を検知する検知装置と、
前記検知装置の検知結果に基づいて、前記セル内に残存する前記正極電解液と前記負極電解液とで、前記正極循環機構及び前記負極循環機構を動作させる制御部と、を備えるレドックスフロー電池システム。 A redox flow battery according to claim 8;
A detection device for detecting a power failure in the power system connected to the redox flow battery;
A redox flow battery system comprising: a control unit that operates the positive electrode circulation mechanism and the negative electrode circulation mechanism with the positive electrode electrolyte and the negative electrode electrolyte remaining in the cell based on a detection result of the detection device. .
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- 2018-03-09 WO PCT/JP2018/009349 patent/WO2019171603A1/en active Application Filing
- 2018-03-09 US US16/976,989 patent/US11183702B2/en active Active
- 2018-03-09 AU AU2018412242A patent/AU2018412242A1/en not_active Abandoned
- 2018-03-09 DE DE112018007254.1T patent/DE112018007254T5/en active Pending
- 2018-03-09 CN CN201880090619.2A patent/CN111837281A/en active Pending
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CN113889638A (en) * | 2020-07-03 | 2022-01-04 | 中国科学院大连化学物理研究所 | Integrated battery structure for all-vanadium redox flow battery, preparation and application |
CN113889638B (en) * | 2020-07-03 | 2023-10-13 | 中国科学院大连化学物理研究所 | Integrated battery structure for all-vanadium redox flow battery, and preparation and application thereof |
WO2023153204A1 (en) * | 2022-02-09 | 2023-08-17 | 三菱重工業株式会社 | Redox flow battery and power supply system comprising redox flow battery |
WO2024070318A1 (en) * | 2022-09-28 | 2024-04-04 | 住友電気工業株式会社 | Cell frame structure, cell stack, and redox flow battery system |
Also Published As
Publication number | Publication date |
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AU2018412242A1 (en) | 2020-09-17 |
JP7249325B2 (en) | 2023-03-30 |
US20210005917A1 (en) | 2021-01-07 |
US11183702B2 (en) | 2021-11-23 |
JPWO2019171603A1 (en) | 2021-02-25 |
DE112018007254T5 (en) | 2020-11-19 |
CN111837281A (en) | 2020-10-27 |
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